CN114729501A - Sheet and method of making the same - Google Patents

Abstract

An object of the present invention is to provide a sheet-like product that has achieved both a soft feel and excellent light resistance, and a method for producing the same. In order to achieve the above-mentioned object, the sheet-like article of the present invention has the following constitution. That is, a sheet-like product containing a polymer elastomer in a fibrous base material, the fibrous base material containing ultrafine fibers having an average single fiber diameter of 0.1 μm or more and 10 μm or less, and the polymer elastic body having a hydrophilic group and containing a polymer The ether diol is used as a constituent, the polymer elastomer has an N-acylurea bond and/or an isourea bond inside, and the sheet-like product satisfies the following conditions 1 and 2. Condition 1: The stiffness in the longitudinal direction specified in the specific standard is 40 mm or more and 140 mm or less; Condition 2: The Martindale abrasion test 2 specified in JIS L 1096:2005 after the light resistance test measured under the conditions specified in the specific standard The wear loss at 10,000 cycles is 25 mg or less.

Description

Sheet and method of making the same

technical field

The present invention relates to a sheet-like article and a method for producing the same, particularly a sheet-like article excellent in flexibility and light resistance, and a method for producing the same.

Background technique

Sheets mainly composed of fibrous substrates such as non-woven fabrics and polyurethane have excellent characteristics that natural leather does not have, and have been widely used in various applications such as artificial leather. In particular, sheets using a polyester-based fibrous base material are excellent in formability, and their use in applications such as clothing materials, seat covers, and automotive interior materials has been increasing year by year.

When producing such a sheet-like product, a combination of the following steps is usually employed: impregnating a fibrous base material with an organic solvent solution of polyurethane, and then immersing the obtained fibrous base material in water or an organic solvent which is a non-solvent for polyurethane In an aqueous solution, the polyurethane is wet coagulated. In this case, a water-miscible organic solvent such as N,N-dimethylformamide can be used as an organic solvent used as a solvent for polyurethane, but in general, organic solvents are highly harmful to the environment, so when manufacturing a sheet-like product , a method that does not use organic solvents is strongly required.

As a specific solution, a method of using a water-dispersed polyurethane obtained by dispersing a polyurethane resin in water instead of a conventional organic solvent-based polyurethane has been studied. However, a sheet-like product solidified by using the water-dispersed polyurethane usually has a texture. Easy to harden problem.

One of the main reasons is that the two methods of solidification are different. That is, the coagulation method of polyurethane using an organic solvent is a so-called wet coagulation method in which the polyurethane molecules dissolved in the organic solvent are substituted with water to solidify, and when viewed in the form of a polyurethane film, a porous film with a low density is formed. . Therefore, when the fibrous base material is impregnated with polyurethane and solidified, the bonding area between the fibers and the polyurethane is reduced, and a soft sheet is formed.

On the other hand, the mainstream coagulation method of the water-dispersed polyurethane is a wet-heat coagulation method in which the hydration state of the water-dispersed polyurethane dispersion is destroyed mainly by heating, and the polyurethane emulsions are coagulated with each other. The membrane structure becomes a non-porous membrane with high density. Therefore, the adhesion between the fibrous base material and the polyurethane becomes tight, and the intertwined portion of the fibers is firmly grasped, so that the texture becomes hard.

Heretofore, in order to obtain a sheet-like product with a soft touch using water-dispersed polyurethane, for example, a method has been proposed in which a thickener is added to a solution containing water-dispersed polyurethane, and a fibrous material impregnated with the solution is treated with hot water. The base material is treated to reduce the size of the polyurethane coating covering the fibrous base material, and to obtain a soft texture (Patent Document 1).

As a method using the coagulation method by the same hot water treatment, there has been proposed a method for obtaining a sheet-like product excellent in heat-and-moisture resistance by performing an aging treatment after dyeing to prevent the deterioration of physical properties due to swelling of polyurethane during dyeing method (Patent Document 2); a method of obtaining a sheet-like product excellent in light resistance and flexibility such as light resistance to yellowing, light resistance and color fastness by applying a water-dispersed polyurethane containing a hindered amine compound (Patent Document 3).

In addition, a method of adjusting the thermal gelation temperature, which is the temperature at which the water-dispersed polyurethane gels, is proposed by dissolving and mixing inorganic salts in the forcibly emulsified nonionic water-dispersed polyurethane, The so-called migration phenomenon in which the particles of the polymer emulsion dispersed in water are concentrated and adhered to the surface layer of the sheet by the movement of the water is suppressed, and a soft feel is obtained (Patent Document 4).

The following method is also proposed: the water-dispersed polyurethane to which polysaccharides are added is impregnated into a sheet, and then heated and dried at two stages of temperature, thereby making the polymer elastomer into a porous structure and making the hand feel soft (patent). Reference 5). In this method, in the drying of the first stage, the polymer elastomer is completely coagulated in a state in which the polysaccharides hold water, and in the drying of the second stage, the elastic polymer is encapsulated in the state of the polymer elastic body in a state of complete coagulation. The water held by the polysaccharides evaporates, and the part where the water held by the polysaccharides exists becomes voids, and a porous structure can be formed.

In addition, a method has been proposed in which a crosslinking agent is applied to a sheet obtained by coagulating a water-dispersed polyurethane, and the sheet is heated to react and maintain the texture before adding the crosslinking agent (Patent Document 6). In this method, irrespective of the coagulation method of the polyurethane, the water-dispersed polyurethane and the crosslinking agent can be reacted, and a state close to the aggregate structure of the original polyurethane can be maintained.

prior art literature

Patent Literature

Patent Document 1: International Publication No. 2015/129602

Patent Document 2: Japanese Patent Laid-Open No. 2017-172074

Patent Document 3: Japanese Patent Laid-Open No. 2000-265052

Patent Document 4: Japanese Patent Laid-Open No. 6-316877

Patent Document 5: Japanese Patent Laid-Open No. 2019-112742

Patent Document 6: International Publication No. 2016/052189

SUMMARY OF THE INVENTION

The problem to be solved by the invention

However, when the sheet is used outdoors, such as for automotive interior materials, the polyurethane that holds the fibers in the sheet is decomposed by ultraviolet rays contained in sunlight, and the sheet is degraded.

Generally, the water-dispersed polyurethane is obtained by the reaction of a polymer polyol, an organic polyisocyanate, and a chain extender, and various properties are exhibited by the components of the polymer polyol. Typical polymer polyols include two types of polyether-based polyols and polycarbonate-based polyols. A sheet-like product using a polyether-based polyurethane is more efficient than a polycarbonate-based polyurethane. A soft touch was obtained, but the light fastness was poor. In order to achieve both a soft feel and light resistance, it is necessary to use a polyether-based polyurethane to improve light resistance to withstand practical use.

In the methods disclosed in Patent Documents 1 to 3, although the hardness of the hand is improved by hot water coagulation, a soft hand can be obtained to a certain extent, but the function of the polyurethane as an adhesive cannot be sufficiently exerted, and the abrasion resistance is insufficient. In the method disclosed in Patent Document 2, since the dye is heated at a high temperature after dyeing, the dye sublimates, which may cause discoloration in actual use, resulting in insufficient light resistance. In addition, in the method disclosed in Patent Document 3, although the inclusion of a hindered amine compound improves light resistance, the inclusion of the compound in the polymer polyol reduces the physical properties of the film, the holding force for fibers becomes weak, and the resistance of the sheet is reduced. Insufficient abrasion resistance. Also, the flexibility is not sufficient.

In addition, in the method disclosed in Patent Document 4, although a soft feel can be achieved by the migration suppression, since the polyurethane resin is not three-dimensionally crosslinked, the fibers cannot be grasped sufficiently, and the abrasion resistance and light resistance are insufficient.

On the other hand, in the method disclosed in Patent Document 5, a porous structure can be obtained by drying in two stages, but the migration phenomenon is not completely suppressed, and the feel is insufficient. In addition, since the polyurethane resin was not three-dimensionally cross-linked, the fibers could not be grasped sufficiently, and the abrasion resistance and light resistance were insufficient.

Alternatively, in the method disclosed in Patent Document 6, after the polyurethane is solidified, the crosslinking agent is impregnated, and the reaction between the polyurethane and the crosslinking agent does not proceed sufficiently, so that a three-dimensional structure based on the polyurethane and the crosslinking agent cannot be sufficiently formed, and the wear resistance is not enough. Properties and light resistance are insufficient.

Then, in view of the background of the above-mentioned prior art, the objective of this invention is to provide the sheet-like object which made the soft touch and the outstanding light resistance compatible, and its manufacturing method.

means of solving problems

In order to achieve the above-mentioned object, the inventors of the present application have conducted repeated studies, and as a result, they have found that a polymer elastic material containing polyether diol as a constituent and using a specific amount of a monovalent cation-containing inorganic salt and a cross-linking agent in combination During the solidification of the body, by adjusting the drying temperature, not only a sheet-like article can be produced in consideration of the environment, but also a sheet-like article excellent in texture and light resistance as compared with the conventional sheet-like article can be obtained, and the present invention has been completed.

That is, an object of the present invention is to solve the above-mentioned problems. The sheet-like article of the present invention is a sheet-like article containing a polymer elastomer in a fibrous base material, and the fibrous base material includes electrodes having an average single fiber diameter of 0.1 μm or more and 10 μm or less. Fine fibers, the polymer elastomer has a hydrophilic group and contains a polyether diol as a constituent, the polymer elastomer has an N-acylurea bond and/or an isourea bond inside, and the sheet satisfies the following Condition 1 and Condition 2.

Condition 1: The stiffness in the longitudinal direction specified in the A method (45° cantilever method) described in JISL 1096:2010 "Woven and Knitted Fabrics" is 40 mm or more and 140 mm or less;

Condition 2: JIS L 0843: 2006 Martindale abrasion test specified in JIS L 1096: 2005 after the light fastness test measured under the condition that the xenon arc amount in JIS L 0843: 2006 is 110 MJ/ ^m2 The wear loss is 25 mg or less.

According to a preferable aspect of the sheet-like article of the present invention, the sheet-like article before the light resistance test has an abrasion loss of 20 mg or less in the Martindale abrasion test 20,000 times specified in JIS L 1096:2010.

According to a preferable aspect of the sheet-like product of this invention, it contains 10 mass % or more of the said polymeric elastomer.

According to a preferable aspect of the sheet-like article of the present invention, the aforementioned sheet-like article also satisfies the following condition 3.

Condition 3: The raised surface of the sheet-like product was placed on a hot plate heated to 150° C., and the retention rate of the L value when pressed with a pressing load of 2.5 kPa for 10 seconds was 90% or more and 100% or less.

The manufacturing method of the sheet-like object of this invention is the manufacturing method of the sheet-like object which includes the following steps (1)-(4) in this order.

(1) A polymer elastomer impregnation step in which a fibrous base material containing ultrafine fiber-developing fibers is impregnated with an aqueous dispersion, followed by heat treatment at a temperature of 120° C. or higher and 180° C. or lower, and the aqueous dispersion liquid is Contains a polymer elastomer, a monovalent cation-containing inorganic salt, and a cross-linking agent, wherein the polymer elastomer has a hydrophilic group and contains a polyether diol as a constituent, relative to 100 mass of the polymer elastomer parts, the content of the monovalent cation-containing inorganic salt in the aforementioned aqueous dispersion is more than 10 parts by mass and less than 50 parts by mass;

(2) an ultrafine fiber development step, wherein the ultrafine fiber development type fibers are subjected to alkali treatment to develop the ultrafine fibers;

(3) a drying step, wherein heat treatment is performed at a temperature of 120°C or higher and 180°C or lower;

(4) Raising process in which at least one surface of the non-raised sheet-like object is subjected to a raising treatment to form piles on the surface.

According to a preferable aspect of the manufacturing method of the sheet-like object of this invention, it further includes the dyeing process which dyes a non-fluffed sheet-like object or a sheet-like object after the said drying process.

According to a preferable aspect of the manufacturing method of the sheet-like object of this invention, the said inorganic salt containing a monovalent cation is sodium chloride and/or sodium sulfate.

According to a preferable aspect of the manufacturing method of the sheet-like object of this invention, the said crosslinking agent is a carbodiimide type crosslinking agent.

Invention effect

ADVANTAGE OF THE INVENTION According to this invention, the sheet-like thing which made the soft touch and outstanding light resistance compatible can be obtained.

Detailed ways

The sheet-like product of the present invention is a sheet-like product containing a polymer elastomer in a fibrous base material, the fibrous base material contains ultrafine fibers having an average single fiber diameter of 0.1 μm or more and 10 μm or less, and the polymer elastic body has hydrophilicity group and contains polyether diol as a constituent, the polymer elastomer has an N-acylurea bond and/or an isourea bond inside, and the sheet-like material satisfies the following conditions 1 and 2.

Condition 1: The stiffness in the longitudinal direction specified in the A method (45° cantilever method) described in JIS L 1096:2010 "Woven and Knitted Fabrics" is 40 mm or more and 140 mm or less.

Condition 2: JIS L 0843: 2006 Martindale abrasion test specified in JIS L 1096: 2005 after the light fastness test measured under the condition that the xenon arc amount in JIS L 0843: 2006 is 110 MJ/ ^m2 The wear loss is 25 mg or less.

The constituent elements will be described in detail below, but the present invention is not limited at all by the scope described below unless the gist is exceeded.

[Extrafine Fiber]

Examples of resins that can be used for the ultrafine fibers used in the present invention include polyester-based resins and polyamide-based resins from the viewpoint of excellent durability, particularly mechanical strength, heat resistance, and light resistance. resin, etc. Specific examples of polyester-based resins include polyethylene terephthalate, polybutylene terephthalate, and polytrimethylene terephthalate. The polyester-based resin can be obtained from, for example, a dicarboxylic acid and/or an ester-forming derivative thereof and a diol.

As the dicarboxylic acid and/or its ester-forming derivative used for the polyester-based resin, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyl-4, 4'-dicarboxylic acid and its ester-forming derivatives, etc. In addition, the ester-forming derivative as used in the present invention refers to lower alkyl esters of dicarboxylic acids, acid anhydrides, acid chlorides, and the like. Specifically, methyl ester, ethyl ester, hydroxyethyl ester, etc. are preferably used. As the dicarboxylic acid and/or its ester-forming derivative used in the present invention, a more preferred embodiment is terephthalic acid and/or its dimethyl ester.

As a diol used for the said polyester-type resin, ethylene glycol, 1, 3- propanediol, 1, 4- butanediol, cyclohexane dimethanol, etc. are mentioned. Among them, ethylene glycol is preferably used.

When a polyamide-based resin is used as the resin for the ultrafine fibers, polyamide 6, polyamide 66, polyamide 56, polyamide 610, polyamide 11, polyamide 12, copolyamide, and the like can be used.

The resin used for the ultrafine fibers can contain inorganic particles such as titanium oxide particles, lubricants, pigments, heat stabilizers, ultraviolet absorbers, conductive agents, heat storage agents, antibacterial agents, and the like according to various purposes.

In addition, the resin used for the ultrafine fibers preferably contains components derived from biomass resources.

As the biomass resource-derived component in the case of using a polyester-based resin as the resin used for the ultrafine fibers, a biomass resource-derived component can be used as its constituent dicarboxylic acid or its ester-forming derivative. However, from the viewpoint of reducing the environmental load, it is preferable to use both the dicarboxylic acid or its ester-forming derivative and the diol derived from biomass resources. Element.

As a component derived from biomass resources when a polyamide resin is used as the resin used for the ultrafine fibers, it is preferable from the viewpoints that the raw materials derived from biomass resources and the physical properties of the fibers can be obtained economically and advantageously. Polyamide 56, polyamide 610, and polyamide 11 are used.

As the cross-sectional shape of the ultrafine fibers, either a circular cross-section or a special-shaped cross-section can be adopted. Specific examples of the deformed cross section include polygons such as elliptical, flat, and triangular, fan-shaped, and cross-shaped.

In the present invention, it is important that the average single fiber diameter of the ultrafine fibers is 0.1 μm or more and 10 μm or less. By making the average single fiber diameter of the ultrafine fibers 10 μm or less, preferably 7 μm or less, and more preferably 5 μm or less, the sheet-like product can be made more flexible. In addition, the quality of the pile can be improved. On the other hand, when the average single fiber diameter of the ultrafine fibers is 0.1 μm or more, preferably 0.3 μm or more, and more preferably 0.7 μm or more, it is possible to obtain a sheet-like shape with excellent color development after dyeing when dyeing is performed. thing. In addition, it is possible to improve the ease of dispersibility and the ease of bulkiness of the ultrafine fibers that are present in bundles during the raising process by buffing.

The average single fiber diameter referred to in the present invention is measured by the following method. which is,

(1) The cross section cut|disconnected in the thickness direction of a sheet-like object was observed with a scanning electron microscope (SEM).

(2) The fiber diameters of 50 arbitrary ultrafine fibers in the observation plane were measured in three directions in each ultrafine fiber cross section. Here, in the case of using the ultrafine fibers of the irregular cross-section, first, the cross-sectional area of the single fiber is measured, and the diameter of the circle which becomes the cross-sectional area is calculated by the following formula. The diameter thus obtained was taken as the single fiber diameter of the single fiber.

·Single fiber diameter (μm)=(4×(Cross-sectional area of single fiber (μm ² ))/π)1/2

(3) Calculate the arithmetic mean value (μm) of the total 150 points obtained, and round off to the second decimal place.

[fibrous base material]

The fibrous base material used in the present invention contains the aforementioned ultrafine fibers. In addition, it is permissible to mix ultrafine fibers of different raw materials in the fibrous base material.

As a specific form of the fibrous base material, a nonwoven fabric in which the ultrafine fibers are intertwined, and a nonwoven fabric in which fiber bundles of the ultrafine fibers are intertwined can be used. Among them, it is preferable to use a nonwoven fabric in which fiber bundles of ultrafine fibers are intertwined from the viewpoint of the strength and texture of the sheet. From the viewpoint of flexibility and texture, it is particularly preferable to use a nonwoven fabric in which the ultrafine fibers constituting the fiber bundle of the ultrafine fibers are appropriately separated from each other and have voids. In this way, the nonwoven fabric in which the fiber bundles of the ultrafine fibers are intertwined can be obtained, for example, by intertwining the fibers of the ultrafine fiber development type in advance and then developing the ultrafine fibers. In addition, a nonwoven fabric in which the ultrafine fibers constituting the fiber bundle of the ultrafine fibers are appropriately separated from each other and has voids can be obtained, for example, by using a sea-island type composite fiber that can be formed on the island by removing the sea component. voids are formed between the components.

As the above-mentioned nonwoven fabric, any of a short fiber nonwoven fabric and a long fiber nonwoven fabric may be used, but it is more preferable to use a short fiber nonwoven fabric from the viewpoint of the texture and quality of the sheet.

When using a short fiber nonwoven fabric, it is preferable that the fiber length of a short fiber is the range of 25 mm or more and 90 mm or less. By setting the fiber length to be 25 mm or more, more preferably 35 mm or more, and still more preferably 40 mm or more, it is easy to obtain a sheet-like article excellent in abrasion resistance by interlacing. In addition, by setting the fiber length to be 90 mm or less, more preferably 80 mm or less, and still more preferably 70 mm or less, a sheet-like product excellent in texture and quality can be obtained.

In the present invention, when a nonwoven fabric is used as the fibrous base material, a woven fabric or a knitted fabric can also be inserted, laminated, or lined inside the nonwoven fabric for the purpose of improving strength or the like. The average single fiber diameter of the fibers constituting the above-mentioned woven fabric and knitted fabric is more preferably 0.3 μm or more and 10 μm or less in order to suppress damage at the time of needling and maintain strength.

Polyesters such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and polylactic acid can be used as fibers constituting the aforementioned woven fabrics and knitted fabrics; nylon 6, Synthetic fibers such as polyamides such as nylon 66; regenerated fibers such as cellulose polymers; natural fibers such as cotton and hemp.

[Polymer elastomers]

In the sheet-like product of the present invention, examples of the polymer elastomer include water-dispersed silicone resins, water-dispersed acrylic resins, water-dispersed urethane resins, and copolymers thereof. Among the above, it is preferable to use a water-dispersed urethane resin from the viewpoint of texture.

As the water-dispersed polyurethane resin, a resin obtained by a reaction of a polymer polyol having a number average molecular weight of preferably 500 or more and 5,000 or less, an organic polyisocyanate and a chain extender is preferably used. In addition, in order to improve the stability of the water-dispersed polyurethane dispersion, it is preferable to use a hydrophilic group-containing active hydrogen component in combination. By setting the number average molecular weight of the polymer polyol to be 500 or more, more preferably 1,500 or more, it is possible to easily prevent the texture from becoming hard. In addition, by setting the number average molecular weight to be 5,000 or less, and more preferably 4,000 or less, the strength of the polyurethane serving as the binder can be easily maintained. The case where a water-dispersed polyurethane resin is used as the polymer elastomer will be described below.

(1) Reaction components of water-dispersed polyurethane resin

First, each reaction component of the water-dispersed urethane resin will be described.

(1-1) Polymer polyol

In the sheet-like product of the present invention, the polymer elastomer contains a polyether diol as a constituent. The content of the polyether diol in the polymer polyol is preferably 50% by mass or more of the entire polymer polyol, more preferably 70% by mass or more, and further preferably 90% by mass or more. Specific examples of the polyether diol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like, and a copolyether glycol obtained by combining these. In addition, in this specification, "comprising... as a structural component" means containing as a monomer component and an oligomer component which comprise a polymeric elastomer. Since polyether diol has a high degree of freedom of ether bonds, its glass transition temperature is low and its cohesion is weak, so that polyurethane excellent in flexibility can be easily obtained.

(1-2) Organic diisocyanate

The organic diisocyanates used in the present invention include aromatic diisocyanates having 6 or more and 20 or less carbon atoms, and aliphatic diisocyanates having 2 or more and 18 or less carbon atoms. Isocyanates, alicyclic diisocyanates having from 4 to 15 carbon atoms, araliphatic diisocyanates having from 8 to 15 carbon atoms, modified products of these diisocyanates (carbodiimide-modified products, amino groups) Formate modified product, uretdione modified product, etc.) and mixtures of two or more of them, etc.

Specific examples of the aromatic diisocyanate having 6 to 20 carbon atoms include 1,3- and/or 1,4-phenylene diisocyanate, 2,4- and/2,6-toluene Diisocyanate, 2,4'- and/or 4,4'-diphenylmethane diisocyanate (hereinafter abbreviated as MDI), 4,4'-biphenyl diisocyanate, 3,3'-dimethyl-4 ,4'-biphenyl diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, and 1,5-naphthalene diisocyanate, etc.

Specific examples of the aliphatic diisocyanates having 2 to 18 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanate methylhexanoate, bis(2-isocyanatoethyl)carbonate, and 2-isocyanatoethyl base-2,6-diisocyanate caproate, etc.

Specific examples of the alicyclic diisocyanate having 4 to 15 carbon atoms include isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, cyclohexylene diisocyanate, methyl methacrylate Cyclohexylene diisocyanate, bis(2-isocyanatoethyl)-4-cyclohexylene-1,2-dicarboxylate, and 2,5- and/or 2,6-norbornane diisocyanate, etc.

Specific examples of the araliphatic diisocyanate having 8 to 15 carbon atoms include m- and/or p-xylylene diisocyanate, α,α,α',α'-tetramethyl Xylylene Diisocyanate, etc.

Among the above, preferable organic diisocyanates are alicyclic diisocyanates. In addition, a particularly preferred organic diisocyanate is dicyclohexylmethane-4,4'-diisocyanate.

(1-3) Chain extender

Examples of the chain extender used in the present invention include water, "ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, and diethylene glycol. and "low molecular weight diols such as neopentyl glycol," alicyclic diols such as "1,4-bis(hydroxymethyl)cyclohexane, etc.," aromatic diols such as "1,4-bis(hydroxyethyl)benzene, etc." Diols, aliphatic diamines such as ethylenediamine, alicyclic diamines such as isophoronediamine, aromatic diamines such as 4,4-diaminodiphenylmethane, and benzenediamine Aromatic aliphatic diamines such as methylamine, alkanolamines such as ethanolamine, hydrazine, dihydrazides such as adipic acid dihydrazide and the like, and mixtures of two or more of them.

Preferred chain extenders among the above are water, low molecular weight diols, and aromatic diamines, and more preferred examples include water, ethylene glycol, 1,4-butanediol, and 4,4'-diaminodiphenylmethane. and mixtures of two or more of them.

(2) Additives for water-dispersed polyurethane resins

In the present invention, it is important to add a monovalent cation-containing inorganic salt to the solution containing the water-dispersed polyurethane, for the reasons described below. In addition, colorants such as titanium oxide, ultraviolet absorbers (benzophenone-based, benzotriazole-based, etc.), antioxidants [4,4-butenylidene-bis(3-methyl) Hindered phenols such as phenyl-6-1-butylphenol); various stabilizers such as triphenyl phosphite, organic phosphites such as trichloroethyl phosphite, etc., and inorganic fillers (calcium carbonate, etc.).

(3) Composition of water-dispersed polyurethane resin

In the water-dispersed polyurethane used in the present invention, as a component for making the polyurethane contain a hydrophilic group, for example, a hydrophilic group-containing active hydrogen component is mentioned. Examples of the hydrophilic group-containing active hydrogen component include compounds containing a nonionic group and/or an anionic group and/or a cationic group and active hydrogen.

Examples of compounds having a nonionic group and active hydrogen include polyoxyethylene diol (polyoxyethylene glycol) containing two or more active hydrogen components or two or more isocyanate groups and having a molecular weight of 250 to 9,000 in a side chain. glycol) group, etc., and trihydric alcohols such as trimethylolpropane, trimethylolbutane, and the like.

Examples of compounds having an anionic group and active hydrogen include carboxyl group-containing compounds such as 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 2,2-dimethylolvaleric acid. compounds and their derivatives, 1,3-phenylenediamine-4,6-disulfonic acid, 3-(2,3-dihydroxypropoxy)-1-propanesulfonic acid and other compounds containing sulfonic acid groups and their derivatives, and salts obtained by neutralizing the above compounds with a neutralizing agent.

Examples of the compound containing a cationic group and active hydrogen include tertiary amino group-containing compounds such as 3-dimethylaminopropanol, N-methyldiethanolamine, and N-propyldiethanolamine, and derivatives thereof.

The aforementioned hydrophilic group-containing active hydrogen component can also be used in the form of a salt neutralized with a neutralizing agent.

For the active hydrogen component containing a hydrophilic group used in the polyurethane molecule, from the viewpoint of the mechanical strength and dispersion stability of the water-dispersed polyurethane resin, 2,2-dimethylolpropionic acid, 2,2-dimethylolpropionic acid, 2-Dimethylolbutyric acid and their neutralized salts.

In the present invention, the hydrophilic group in the polymer elastomer refers to a group having active hydrogen. As a specific example of a hydrophilic group, a hydroxyl group, a carboxyl group, a sulfonic acid group, an amino group, etc. are mentioned.

In the present invention, the polymer elastomer has an N-acylurea bond and/or an isourea bond inside. Here, the fact that the polymer elastomer has an N-acylurea bond and/or an isourea bond inside the polymer elastomer means that the polymer elastomer has an N-acylurea bond and/or an isourea bond. In the case of using a water-dispersed polyurethane resin as the polymer elastomer, the N-acylurea bond and/or the isourea bond can pass through, for example, a hydroxyl group and/or a carboxyl group present as the aforementioned hydrophilic group-containing active hydrogen component. , formed by reacting with carbodiimide-based crosslinking agent. As a result, a three-dimensional crosslinked structure based on N-acylurea bond and/or isourea bond, which is excellent in physical properties such as light resistance, heat resistance, and abrasion resistance, and flexibility, is imparted in the molecule of the polymer elastomer, and can be Physical properties such as abrasion resistance are remarkably improved while maintaining the flexibility of the sheet.

It should be noted that, for the presence of the above-mentioned N-acylurea groups and isourea groups in the polymer elastomer, the cross-section of the sheet-like product can be mapped by, for example, time-of-flight secondary ion mass spectrometry (TOF-SIMS analysis) or the like ( Mapping) processing (for example, "TOF.SIMS 5" manufactured by ION-TOF Corporation, etc. as an analytical instrument), infrared spectrum analysis (as an analytical instrument, for example, "FT/IR 4000 series" manufactured by JASCO Corporation, etc.) analysis.

The number average molecular weight of the polymer elastomer used in the present invention is preferably 20,000 or more from the viewpoint of resin strength, and preferably 500,000 or less from the viewpoints of viscosity stability and handleability. The number average molecular weight is more preferably 30,000 or more and 150,000 or less.

The number average molecular weight of the polymer elastomer can be determined by gel permeation chromatography, and is measured under the following conditions, for example.

・Equipment: HLC-8220 manufactured by Tosoh Corporation

Column: Tosoh TSKgel α-M

Solvent: N,N-Dimethylformamide (DMF)

·Temperature: 40℃

Calibration: Polystyrene

A preferred embodiment of the polymer elastomer used in the present invention is to exist inside a fibrous base material from the viewpoint of appropriately holding fibers in a sheet-like article, and preferably having piles on at least one side of the sheet-like article.

[sheets]

It is important that the stiffness in the longitudinal direction of the sheet-like product of the present invention is 40 mm or more and 140 mm or less, as specified in the A method (45° cantilever method) described in JIS L 1096:2010 "Woven and Knitted Fabric Test Methods". By making the stiffness into the above-mentioned range, it is possible to have moderate flexibility and repellency. The stiffness is preferably 50 mm or more, more preferably 55 mm or more, from the viewpoint that a repellent sheet-like product can be obtained, and preferably 120 mm or less, more preferably, from the viewpoint of obtaining a flexible sheet-like product. 110mm or less.

The longitudinal direction of the sheet-like object of the present invention is the direction in which the fluffing treatment is performed on the sheet-like object. As a method of specifying the direction in which the fluffing process is performed, visual confirmation at the time of tracing with a finger, SEM imaging, etc. can be appropriately employed in accordance with the constituent components of the sheet-like object. That is, when tracing with a finger, the direction in which the pile fibers can be made to lie down or stand up is the longitudinal direction. In addition, the surface of the sheet-like object traced with a finger was subjected to SEM imaging, and the direction in which the most lying down pile fibers were oriented was the longitudinal direction. On the other hand, the transverse direction in the sheet-like material of the present invention refers to a direction perpendicular to the longitudinal direction.

In addition, the sheet-like article of the present invention is the Martindale abrasion test specified in JIS L 1096: 2005 after the light fast test measured under the condition that the xenon arc amount of the JIS L 0843: 2006 lightfastness measurement method is 110 MJ/m ² It is important that the wear loss at 20,000 cycles is 25 mg or less. By setting the wear loss after the light resistance test to the above-mentioned range, the deterioration of the polymer elastomer can be suppressed and the appearance of the sheet can be maintained even if it is used for a long time in a severe environment such as exposure to sunlight. The wear loss is preferably 23 mg or less, and more preferably 20 mg or less, from the viewpoint of being able to suppress deterioration of the appearance of the sheet-like object.

The sheet-like article of the present invention preferably has an abrasion loss of 20 mg or less in the Martindale abrasion test specified in JIS L 1096:2010 for 20,000 cycles of the sheet-like article before the light resistance test. By making the abrasion loss before the light resistance test into the above-mentioned range, it becomes easy to suppress hair loss during actual use, deterioration of the appearance, and the like. The wear loss is preferably 18 mg or less, and more preferably 15 mg or less, from the viewpoint of further suppressing hair loss during actual use.

It is preferable that the sheet-like product of this invention contains 10 mass % or more of polymeric elastomers. From the viewpoint of being able to suppress breakage due to tension in the production process, lint during actual use, and the like, the polymer elastomer is more preferably contained in an amount of 12% by mass or more, and even more preferably 15% by mass or more. The upper limit of the content is not particularly limited, but is usually 50% by mass or less, preferably 40% by mass or less, and more preferably 35% by mass or less.

Preferably, the sheet-like product of the present invention also satisfies the following condition 3.

Condition 3: Retention rate of L value when the raised surface of the sheet is placed on a hot plate heated to 150°C and pressed with a pressing load of 2.5 kPa for 10 seconds (hereinafter, it may be abbreviated as L value retention rate only) 90% or more and 100% or less.

Among them, when the L value retention is 90% or more, more preferably 92% or more, and still more preferably 95% or more, the sheet-like product has high heat resistance.

In addition, in this invention, "the raised surface of a sheet-like object" means the surface which raised a sheet-like object. In addition, the L value refers to the L value specified by the International Commission on Illumination (Commission International on Illumination, CIE), and the L value retention rate in the present invention refers to a ratio of a change in lightness under heating and pressing conditions that is small, that is, heating and pressing. It is an indicator of how much the sheet-like substance having a dark color before pressing does not become bright after heating and pressing.

In addition, in this invention, the L value retention rate means the value measured and calculated by the following procedure.

(1) The sheet-like object is cut, and the L value of the cut test piece is measured using a colorimeter (for example, "CR-410" manufactured by KONICA MINOLTA, INC.).

(2) The test piece was placed on a hot plate (for example, "CHP-250DN" manufactured by AS ONECORPORATION., etc.) heated to 150° C. with the raised surface of the test piece facing down.

(3) An indenter adjusted so that the pressing load becomes 2.5 kPa was placed on the test piece, and held for 10 seconds.

(4) Remove the indenter on the test piece, and measure the L value of the raised surface of the test piece with the aforementioned colorimeter.

(5) The L value retention rate was calculated by the following formula.

L value retention rate (%)=(L value measured in (1))/(L value measured in (4))×100

In order to keep the stiffness, wear loss before the light resistance test, and after the light resistance test, and the L value retention rate within the above-mentioned ranges, for example, through the polymer elastomer impregnation process, the ultrafine fiber development process, and the drying process, which will be described later. Make flakes. By impregnating the polymer elastomer and then passing through the ultrafine fiber development step, the gap between the ultrafine fibers and the polymer elastomer can be formed, and a soft texture can be easily obtained. In addition, for example, by performing heat treatment (aging treatment) at a temperature of 120° C. or higher and 180° C. or lower in the drying step, the particles of the polymer elastomer can be aggregated with each other, and light resistance, abrasion resistance, and heat resistance can be easily improved. In addition, by setting the thermal solidification temperature of the aqueous dispersion in the range described later, the localization (migration) of the polyurethane on the sheet surface accompanying the evaporation of moisture can be suppressed, and the L value retention rate can be improved.

[Manufacturing method of sheet]

Next, the manufacturing method of the sheet-like object of this invention is demonstrated.

The manufacturing method of the sheet-like object of this invention includes the following processes (1)-(4) in this order.

(1) A polymer elastomer impregnation step in which a fibrous base material containing ultrafine fiber-developing fibers is impregnated with an aqueous dispersion, followed by heat treatment at a temperature of 120° C. or higher and 180° C. or lower, and the aqueous dispersion liquid is Contains a polymer elastomer, a monovalent cation-containing inorganic salt, and a cross-linking agent, wherein the polymer elastomer has a hydrophilic group and contains a polyether diol as a constituent, relative to 100 mass of the polymer elastomer parts, the content of the monovalent cation-containing inorganic salt in the aforementioned aqueous dispersion is more than 10 parts by mass and less than 50 parts by mass;

(2) an ultrafine fiber development step, wherein the ultrafine fiber development type fibers are subjected to alkali treatment to develop the ultrafine fibers;

(3) A drying step in which heat treatment is performed at a temperature of 120° C. or higher and 180° C. or lower

(4) Raising process in which at least one surface of the non-raised sheet-like object is subjected to a raising treatment to form piles on the surface.

In this invention, a "non-fluffed sheet-like object" means the sheet-like object before the fluffing process obtained by the method which comprises at least the said process (1)-(3) in this order.

In the present invention, as a means for obtaining ultrafine fibers, it is a preferable aspect to use ultrafine fiber development type fibers. The nonwoven fabric in which the ultrafine fiber bundles are intertwined can be obtained by making the fibers ultrafine after intertwining the ultrafine fiber-developing fibers in advance to prepare a nonwoven fabric.

As the ultrafine fiber-appearing type fiber, moderate voids can be provided between the island components, that is, between the ultrafine fibers inside the fiber bundle when the sea component is removed, and therefore, from the viewpoints of the texture and surface quality of the sheet, it is preferable to use The sea-island type conjugate fiber is composed of two components (two or three components when the island fiber is a core-sheath conjugate fiber) having different solubility in a solvent as the sea component and the island component, and the above-mentioned components are mixed with a solvent or the like. The sea component is dissolved and removed, whereby the island component is formed into ultrafine fibers.

As the sea-island type composite fiber, from the viewpoint of obtaining ultrafine fibers with a uniform single fiber diameter, it is preferable to use a nozzle for the sea-island type composite fiber and use two components, a sea component and an island component (the island fiber is the core). In the case of sheath composite fibers, it is a form of a polymer array in which three components) are aligned and spun.

As the sea component of the sea-island type composite fiber, polyethylene, polypropylene, polystyrene, copolyester copolymerized with sodium isophthalate sulfonate, polyethylene glycol, etc., polylactic acid, etc. , from the viewpoint of ease of dissolution, etc., polystyrene and copolyester are preferably used.

It is a preferable form to dissolve and remove the sea component after providing the polymer elastomer. Described below.

The mass ratio of the sea component and the island component in the sea-island type conjugate fiber used in the present invention is preferably in the range of: sea component:island component=10:90 to 80:20. When the mass ratio of the sea component is 10% by mass or more, it is easy to sufficiently miniaturize the island component. In addition, when the mass ratio of the sea component is 80 mass or less, the ratio of the eluted component is small, so that productivity is improved. The mass ratio of the sea component and the island component is more preferably in the range of: sea component:island component=20:80 to 70:30.

In addition, the fiber interwoven body is preferably in the form of a non-woven fabric. As described above, it can be used regardless of whether it is a short-fiber non-woven fabric or a long-fiber non-woven fabric. It is preferable that there are more fibers in the thickness direction of the fibrous nonwoven fabric than a long-fiber nonwoven fabric, since a high density feeling of the surface of the fibrous base material during raising can be obtained.

When using the staple fiber nonwoven fabric as the fiber interwoven body, it is preferable to crimp the obtained ultrafine fiber-developing fibers, cut them into predetermined lengths, and process them to obtain raw cotton. A known method can be used for the crimping process and the cutting process.

Next, the obtained raw cotton is made into a fiber web by cross-lapping or the like, and is intertwined to obtain a short-fiber nonwoven fabric. As a method of a short-fiber nonwoven fabric obtained by entangling a fiber web, a needle punching process, a waterjet punching process, or the like can be used.

Furthermore, the obtained short fiber nonwoven fabric and the woven fabric are laminated and integrated by interlacing. In the interweaving and integration of the staple fiber nonwoven fabric and the woven fabric, the woven fabric is laminated on one or both sides of the staple fiber nonwoven fabric, or the woven fabric is sandwiched between a plurality of staple fiber nonwoven fabric webs, and then passed through a needle Needle treatment, spunlace treatment, etc. entangle the fibers of the staple fiber nonwoven fabric and the woven fabric with each other.

It is preferable that the apparent density of the staple fiber nonwoven fabric containing the conjugated fibers (ultrafine fiber developing type fibers) after the needling treatment or the hydroentangling treatment is 0.15 g/cm ³ or more and 0.45 g/cm ³ or less. By making the apparent density preferably 0.15 g/cm ³ or more, the fibrous base material can obtain sufficient morphological stability and dimensional stability. On the other hand, by setting the apparent density to preferably 0.45 g/cm ³ or less, it is possible to maintain a sufficient space for providing the polymer elastomer.

From the viewpoint of densification, the nonwoven fabric obtained in this way is preferably shrunk by dry heat, moist heat, or both, and further densified. In addition, the nonwoven fabric can also be compressed in the thickness direction by calendering or the like.

The method for producing a sheet of the present invention includes: (1) a step of impregnating a polymer elastomer, in which a fibrous base material containing ultrafine fiber-developing fibers is impregnated with an aqueous dispersion, and then the temperature is 120° C. or higher and 180° C. or lower. The aqueous dispersion liquid contains a polymer elastomer, an inorganic salt containing a monovalent cation and a crosslinking agent, wherein the polymer elastomer has a hydrophilic group and contains a polyether diol as a constituent As a component, the content of the monovalent cation-containing inorganic salt in the aqueous dispersion is 10 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the polymer elastomer.

In the manufacturing method of the sheet-like object of this invention, the polymeric elastomer which has a hydrophilic group and contains a polyether diol as a structural component is provided to a fibrous base material. When a nonwoven fabric is used as a fibrous base material, whether it is a nonwoven fabric containing a composite fiber or a nonwoven fabric made of ultrafine fibers, the provision of a polymer elastic body can be performed.

In the manufacturing method of the sheet-like object of this invention, the said polymeric elastomer contains polyether diol as a structural component. The reason is the same as that described in the item of the aforementioned (1-1) Polymer polyol.

In the manufacturing method of the sheet-like object of this invention, the dry heat coagulation method which heat-processes at the temperature of 120 degreeC or more and 180 degrees C or less is used for the coagulation|solidification after providing a polymeric elastomer. As for other coagulation methods, for example, a hot water coagulation method in which a polymer elastomer is coagulated in hot water, the polymer elastomer diffuses in the hot water, and a part thereof falls off, so there is a concern in workability. In addition, in the acid coagulation method of coagulating a polymer elastomer with an acid, it is necessary to neutralize the acid solution remaining in the sheet, which is also not preferable in terms of processing workability. On the other hand, the dry heat coagulation method applied in the present invention is a very simple method of heat-treating a sheet impregnated with a polymer elastomer with a hot air dryer or the like, and there is no concern that the polymer elastomer falls off. It is a method with excellent workability.

In the manufacturing method of the sheet-like object of this invention, the heating temperature at the time of dry heat solidification is 120 degreeC or more and 180 degrees C or less. The heating temperature is more preferably 140°C or higher. This is because the polymer elastic body can be rapidly solidified, and the unevenness of the polymer elastic body to the lower surface of the sheet due to its own weight can be suppressed. Further, in the present invention, a crosslinking agent is required to be used in combination, but by setting the above temperature, the crosslinking reaction can be sufficiently accelerated, a three-dimensional network structure can be formed, and physical properties, light resistance, and heat resistance can be improved. The heating temperature is more preferably 175°C or lower. This is because thermal degradation of the polymer elastomer can be suppressed.

From the viewpoint of the storage stability of the aqueous dispersion, the concentration of the polymer elastomer in the aqueous dispersion (the content of the polymer elastomer in 100% by mass of the aqueous dispersion) is preferably 10% by mass or more and 50% by mass or less, More preferably, it is 15 mass % or more and 40 mass % or less.

The aqueous dispersion used in the present invention may contain 40 mass % or less of a water-soluble organic solvent in 100 mass % of the aqueous dispersion in order to improve storage stability and film-forming properties, and from the viewpoint of maintaining the film-forming environment, etc. It is preferable that content of an organic solvent shall be 1 mass % or less.

In the manufacturing method of the sheet-like object of this invention, the inorganic salt containing a monovalent cation is contained in an aqueous dispersion. By containing a monovalent cation-containing inorganic salt, heat-sensitive coagulation properties can be imparted to the aqueous dispersion. In the present invention, the thermal coagulation property refers to a property in which the fluidity of the aqueous dispersion decreases and coagulation occurs when a certain temperature (thermal coagulation temperature) is reached when the aqueous dispersion is heated.

In the method for producing a sheet of the present invention, after applying the aqueous dispersion to the fibrous base material, heat treatment is performed at a temperature of 120° C. or higher and 180° C. or lower to coagulate the fibrous base material with high dry heat. Molecular Elastomers.

When the polymeric elastomer does not have heat-sensitive coagulation properties, the polymeric elastomer migrates to the sheet surface as the water evaporates and migrates. In addition, since the polymer elastic body coagulates in a state where the polymer elastic body is concentrated around the fibers as the water evaporates, the polymer elastic body covers the surrounding of the fibers and has a structure in which the movement is strongly restricted. Thereby, the feel of the sheet-like product is remarkably hardened.

The heat-sensitive coagulation temperature of the aqueous dispersion is preferably 55°C or higher and 80°C or lower. The storage stability of the aqueous dispersion is good, and the adhesion of the polymer elastomer to the equipment during handling can be suppressed, so the more preferable heat-sensitive temperature is 60°C or higher. The migration phenomenon of the polymer elastomer to the surface layer of the fibrous base material can be suppressed, and the polymer elastomer can be formed and wet-coagulated by coagulating the polymer elastomer before the moisture from the fibrous base material evaporates. On the other hand, a structure similar to the obtained case, that is, a structure in which the polymer elastomer does not strongly restrict the fibers, and can achieve good flexibility and repellency, it is more preferable that the thermal coagulation temperature is 70°C or lower.

In the present invention, it is important to use a monovalent cation-containing inorganic salt among the inorganic salts used as the heat-sensitive coagulant. The aforementioned monovalent cation-containing inorganic salt is preferably sodium chloride and/or sodium sulfate. In the conventional method, inorganic salts having divalent cations such as magnesium sulfate and calcium chloride are suitably used as heat-sensitive coagulants. Even if these inorganic salts are added in small amounts, the stability of the aqueous dispersion is greatly affected. Therefore, Depending on the type of polymer elastomer, it is difficult to strictly control the thermosensitive gelation temperature by adjusting the amount of addition thereof, and there are problems such as concerns about gelation during adjustment of the aqueous dispersion and storage. On the other hand, the inorganic salt containing a monovalent cation with a small ionic valence has little influence on the stability of the aqueous dispersion, and by adjusting the amount of addition, the thermosensitive coagulation temperature can be tightly controlled while ensuring the stability of the aqueous dispersion .

Further, in the present invention, it is important that the content of the monovalent cation-containing inorganic salt in the aqueous dispersion is 10 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the polymeric elastomer. By setting the content to 10 parts by mass or more, ions present in a large amount in the aqueous dispersion uniformly act on the polymer elastomer particles, and coagulation can be quickly completed at a specific heat-sensitive coagulation temperature. Accordingly, when the polymer elastomer is coagulated in a state where a large amount of water is contained in the fibrous base material as described above, a more remarkable effect can be obtained. As a result, a structure very similar to that obtained by wet coagulation of the solvent-based polymer elastomer is formed, and favorable flexibility and repellency can be realized. In addition, by setting the amount of addition as described above, the inorganic salt serves as an inhibitor when the polymer elastomer particles are melted, and the curing of the polymer elastomer due to continuous film formation can also be suppressed. On the other hand, by making content into 50 mass parts or less, the continuous film structure of an appropriate high molecular elastomer can remain|survive, and the fall of physical property can be suppressed. In addition, the stability of the aqueous dispersion can also be maintained.

In the manufacturing method of the sheet-like object of this invention, it is important that an aqueous dispersion contains a crosslinking agent. Physical properties such as abrasion resistance can be improved by introducing a three-dimensional network structure into the polymer elastomer by a crosslinking agent. Furthermore, by using the aforementioned inorganic salt containing a monovalent cation in combination, the coagulation of the polymer elastomer and the reaction between the polymer elastomer and the cross-linking agent can proceed simultaneously, and it is possible to pass the dense three-dimensional network structure. Formation and control of the bonding structure of fibers make the sheet soft and at the same time achieve high physical properties, high light resistance, and high heat resistance of the sheet. That is, in addition to improving the physical properties, light resistance, and heat resistance of the sheet, the combined use of a monovalent cation-containing inorganic salt and a crosslinking agent, and the control of the heating temperature during dry heat coagulation are necessary and indispensable.

The crosslinking agent is preferably a carbodiimide-based crosslinking agent, because the polymer elastomer obtained after the reaction is excellent in light resistance, heat resistance, and abrasion resistance, and also has good flexibility.

The method for producing a sheet of the present invention includes (2) an ultrafine fiber development step in which the ultrafine fiber development type fibers are subjected to alkali treatment to develop the ultrafine fibers. By performing the alkali treatment after imparting the polymer elastomer, voids due to the components dissolved by the alkali treatment are formed between the polymer elastomer and the ultrafine fibers, so that the polymer elastomer does not directly hold the ultrafine fibers, and the flakes are formed. feel becomes softer.

When the sea-island type composite fiber is used as the ultrafine fiber-developing type fiber, the fiber miniaturization treatment (sea removal treatment) can be performed, for example, by immersing the sea-island type composite fiber in a solvent and squeezing the liquid. As the solvent for dissolving the sea component, an alkaline aqueous solution such as sodium hydroxide or hot water can be used.

In the ultrafine fiber development step, devices such as a continuous dyeing machine, a vibro-washer type de-sealing machine, a liquid flow dyeing machine, a wince dyeing machine, and a jigger dyeing machine can be used.

After the ultrafine fiber development step, it is preferable to perform a sufficient washing step after the alkali treatment. By going through the washing step, the alkali and monovalent cation-containing inorganic salt adhering to the sheet can be processed without remaining on the sheet, and processing can be performed without affecting production facilities. In consideration of environmental aspects and safety, water is preferably used for the cleaning liquid.

The manufacturing method of the sheet-like object of this invention includes (3) a drying process which heat-processes at the temperature of 120 degreeC or more and 180 degrees C or less. In the ultrafine fiber development step, the bonds of the polymer elastomer are partially released by a solvent that dissolves components other than the ultrafine fibers in the ultrafine fiber development type fibers, and an aging treatment by drying is performed, whereby the polymer elastomer is formed. The particles aggregated with each other can further improve physical properties such as light resistance, abrasion resistance, and heat resistance.

In the manufacturing method of the sheet-like object of this invention, the heating temperature in the aging process by drying is 120 degreeC or more and 180 degrees C or less. In order to enhance the effect of the aging treatment and to increase physical properties such as light resistance, abrasion resistance, and heat resistance, the temperature is preferably 140°C or higher, and more preferably 150°C or higher. In order to suppress thermal degradation of the polymer elastomer, the temperature is preferably 175°C or lower, and more preferably 170°C or lower.

It is preferable that the manufacturing method of the sheet-like object of this invention further includes the dyeing process which dyes a non-fluffed sheet-like object or a sheet-like object after the said drying process. As the dyeing treatment, various methods commonly used in this field can be employed, for example, dip dyeing treatment such as a jig dyeing machine, a liquid flow dyeing treatment using a liquid dyeing machine, a thermosol dyeing treatment using a continuous dyeing machine, or the like, or Printing and dyeing of pile surface based on roller printing and dyeing, screen printing and dyeing, inkjet printing and dyeing, sublimation printing and dyeing and vacuum sublimation printing and dyeing. Among them, a flow dyeing machine is preferably used because a rubbing effect can be imparted while dyeing the non-fluffed sheet or sheet to make the non-fluffed sheet or sheet soft. Moreover, various resin finishing can be performed after dyeing as needed.

The dyeing temperature varies depending on the type of fiber, but is preferably 80°C or higher and 150°C or lower. By making the dyeing temperature 80°C or higher, more preferably 110°C or higher, the fibers can be dyed efficiently. On the other hand, by setting the dyeing temperature to be 150° C. or lower, more preferably 130° C. or lower, deterioration of the polymer elastomer can be prevented.

The dye used in the present invention may be selected according to the type of fibers constituting the fibrous base material, and is not particularly limited. For example, in the case of polyester fibers, disperse dyes can be used, and in the case of polyamide fibers, acid can be used Dyes, gold-containing dyes, and combinations thereof can also be used. In the case of dyeing with disperse dyes, reduction washing may be performed after dyeing.

It is also a preferred way to use dyeing auxiliaries during dyeing. By using a dyeing assistant, the uniformity and reproducibility of dyeing can be improved. In addition, treatment with a finishing agent such as a softener such as silicone, an antistatic agent, a water repellent, a flame retardant, a lightfast agent, and an antibacterial agent can be performed in the same bath as the dyeing or after the dyeing.

In the present invention, from the viewpoint of production efficiency, half-cutting in the thickness direction is preferable before or after the dyeing step.

The manufacturing method of the sheet of the present invention (both before and after the dyeing step) includes: (4) a raising step in which at least one surface of the non-raised sheet is raised to form piles on the surface. The method of forming the pile is not particularly limited, and various methods commonly performed in the art, such as polishing by sandpaper or the like, can be used. When the pile length is too short, it is difficult to obtain a beautiful appearance, and when it is too long, pilling tends to occur. Therefore, the pile length is preferably 0.2 mm or more and 1.0 mm or less.

Moreover, in one form of this invention, silicone etc. may be provided as a lubricant to a non-raised sheet-like material before raising process. By adding a lubricant, fluffing by surface grinding can be facilitated, and surface quality can be very good, which is preferable. In addition, an antistatic agent can be added before the raising treatment, and by providing an antistatic agent, the grinding powder generated from the sheet-like object by grinding is less likely to be deposited on the sandpaper, which is a preferable aspect.

Moreover, in one form of this invention, designability can be given to the surface as needed. For example, post-processing such as drilling processing such as perforation, embossing processing, laser processing, Pinsonic processing (Pinsonic processing), and printing processing can be performed.

Example

Next, the sheet-like article of the present invention will be further specifically described using examples, but the present invention is not limited to the following examples.

[Evaluation method]

(1) The average single fiber diameter of the sheet:

The cross section perpendicular to the thickness direction including fibers of the sheet-like product was observed at 3000 magnification using a scanning electron microscope (SEM, VE-7800 manufactured by KEYENCE Corporation), and 50 sheets were randomly extracted in a field of view of 30 μm×30 μm. The fiber diameter was measured to the first decimal place in μm.

The diameters of a total of 150 single fibers were measured at three locations, and the average value was calculated to the first decimal place. When fibers with a fiber diameter exceeding 50 μm were mixed, the fibers were regarded as not belonging to the ultrafine fibers, and were excluded from the measurement target of the average fiber diameter. In addition, when the ultrafine fiber has an irregular cross-section, as described above, first, the cross-sectional area of the single fiber is measured, and the diameter when the cross-section is compared to a circle is calculated to obtain the diameter of the single fiber. The average value of the statistical population was calculated as the average single fiber diameter.

(2) Solidification temperature of aqueous dispersion

20 g of the aqueous dispersions containing the polymer elastomers prepared in the respective Examples and Comparative Examples were put into a test tube with an inner diameter of 12 mm, and the thermometer was inserted so that the tip was below the liquid surface, the test tube was sealed, and the It was immersed in the warm water bath of the temperature of 95 degreeC so that the liquid level of the aqueous dispersion liquid might be below the liquid level of the warm water bath. The temperature rise in the test tube was checked with a thermometer, and the test tube was lifted up and shaken appropriately to the extent that the liquid level of the aqueous dispersion could be checked for fluidity within 5 seconds every time. The temperature at which fluidity is lost is taken as the solidification temperature. This measurement was performed three times for each type of aqueous dispersion, and the average value was calculated.

(3) Evaluation of the softness of the sheet:

According to the A method (45° cantilever method) described in 8.21 "Stiffness" of 8.21 "Stiffness" of JIS L 1096:2010 "Test methods for fabrics of woven and knitted fabrics", five test pieces with a longitudinal direction of 2 × 15 cm were prepared , placed on a water platform with an inclined surface at an angle of 45°, the test piece was slid, the scale when the center point of one end of the test piece was in contact with the inclined surface was read, and the average value of 5 sheets was obtained.

(4) Wear evaluation of sheet-like objects

Wear evaluation was performed based on JIS L 1096:2010. As a Martindale abrasion tester, Model 406 manufactured by James H. Heal & Co. was used, and as a standard rubbing cloth, ABRASTIVE CLOTH SM25 of the company was used. A load of 12 kPa was applied to the sheet before and after the light resistance test described later, and the number of abrasions was 20,000 times. The wear loss was calculated by the following formula using the mass of the sheet before and after wear.

Wear loss (mg) = mass before wear (mg) - mass after wear (mg)

It should be noted that, with regard to the wear loss, the value obtained by rounding off the value to the first decimal place is used as the wear loss.

(5) Light resistance test of sheet

According to JIS L 0843:2006 light fastness measurement method (B method, 5th exposure method), irradiation was performed under the conditions which adjusted the measurement time so that the xenon arc irradiation amount might be 110 MJ/m< ² >.

(6) Identification of bond types in polymer elastomers

The polymer elastomer isolated from the above-mentioned sheet-like product was identified by infrared spectrum analysis using FT/IR4000 series manufactured by JASCO Corporation.

(7) L value retention rate

As a hot plate, "CHP-250DN" manufactured by AS ONE CORPORATION. was used, and as a colorimeter, "CR-410" manufactured by KONICAMINOLTA, INC. was used, and the measurement and calculation were performed by the aforementioned methods.

(8) Determination of the type and content of inorganic salts contained in the sheet:

The sheet-like product was immersed in N,N-dimethylformamide overnight, and the solution obtained by elution of the polymer elastomer and the inorganic salt was concentrated and solidified by heating and drying at 140°C. Distilled water was added to the obtained solid matter to dissolve only the inorganic salt. The inorganic salt-containing aqueous solution was heated and dried, and the amount of the inorganic salt contained in the sheet was further measured. In addition, after heating and drying the solidified polymer elastomer, the mass was measured, and the mass of the inorganic salt was calculated in comparison with the mass of the polymer elastomer. However, from the viewpoint of the validity of the numerical value, when it is less than 0.1 mass % compared with the polymer elastomer, it is regarded as being below the detection lower limit.

About the kind of inorganic salt, the said aqueous solution containing the inorganic salt was identified using the ion chromatograph of "ICS-3000 type" made by Dionex.

[Manufacturing method of nonwoven fabric A for fibrous base materials]

8 mol % of SSIA (sodium isophthalate-5-sulfonate) copolyester was used as the sea component, polyethylene terephthalate was used as the island component, the sea component was 20 mass %, and the island component was 80 The composite ratio in mass % yielded a sea-island type composite fiber with 16 islands/1 filament and an average single fiber diameter of 20 μm. The obtained sea-island type composite fiber was cut into a fiber length of 51 mm as a staple fiber (staple), a fiber web was formed by a carding machine and a cross-lap, and a needle punching process was performed to manufacture a 700 g/m ² weight per unit area and a thickness of 3.0 mm. Non-woven. The nonwoven fabric obtained in this way was dipped in hot water at a temperature of 98° C. for 2 minutes to shrink it, and dried at a temperature of 100° C. for 5 minutes to prepare a nonwoven fabric A for a fibrous base material.

[Manufacturing method of nonwoven fabric B for fibrous base materials]

8 mol % of SSIA (sodium 5-sulfoisophthalate) copolyester was used as the sea component, polyethylene terephthalate was used as the island component, the sea component was 43% by mass, and the island component was 57% The composite ratio in mass % yielded a sea-island type composite fiber with 16 islands/1 filament and an average single fiber diameter of 20 μm. The obtained sea-island type composite fiber was cut into short fibers with a fiber length of 51 mm, a fiber web was formed by a carding machine and a cross-lap, and a nonwoven fabric with a weight per unit area of 550 g/m ² and a thickness of 2.9 mm was produced by needle punching . The nonwoven fabric obtained in this way was dipped in hot water at a temperature of 98° C. for 2 minutes to shrink it, and dried at a temperature of 100° C. for 5 minutes to prepare a nonwoven fabric B for a fibrous base material.

[Manufacturing method of polymer elastomer]

As the polyol, polytetramethylene ether glycol (referred to as PTMG in the table) having a number-average molecular weight (Mn) of 2,000 was used, and 2,2-diol was used as a component containing MDI and a hydrophilic group in the isocyanate. Methylolpropionic acid, prepolymer made in toluene solvent. Ethylene glycol and ethylenediamine were added as chain extenders, and nonylphenol polyoxyethylene ether and water were added as external emulsifiers, followed by stirring. Toluene was removed under reduced pressure to obtain an aqueous dispersion of a polymer elastomer.

[Example 1]

(non-woven fabric)

As the nonwoven fabric, the nonwoven fabric A for fibrous substrates was used.

(Addition of high molecular elastomer)

With respect to 100 parts by mass of the polymer elastomer, 20 parts by mass of sodium sulfate (referred to as "Na ₂ SO ₄ " in Table 1) as a heat-sensitive coagulant was added, and 3 parts by mass of a carbodiimide-based crosslinking agent was added, The whole was adjusted to 12 mass % of solid content with water, and the aqueous dispersion liquid containing a polymeric elastomer was obtained. The thermal coagulation temperature is 70°C. The obtained nonwoven fabric A for a fibrous base material was immersed in the aforementioned aqueous dispersion, and then dried with hot air at a temperature of 160° C. for 20 minutes to obtain a sheet-like product with a high percentage of 100% by mass in the sheet-like product. The nonwoven fabric having a thickness of 2.10 mm was provided with a high molecular elastic body so that the molecular elastic body was 20% by mass.

(Extra-fine fiber display processing)

The obtained polymer elastomer-provided nonwoven fabric was immersed in a sodium hydroxide aqueous solution having a concentration of 8 g/L heated to a temperature of 95° C. and treated for 5 minutes, thereby removing the sea component of the sea-island type composite fiber. Then, the sodium hydroxide aqueous solution adhering to the nonwoven fabric was immersed in water, washed for 30 minutes, and dried with a dryer at 160° C. for 30 minutes to obtain a sheet containing ultrafine fibers (a polymer elastomer-imparting sheet).

(Dyeing・Finishing)

The obtained deseamed polymer elastomer-imparting sheet was half-cut in a direction perpendicular to the thickness direction, and the opposite side of the half-cut surface was ground with a circular sandpaper of No. 180 sandpaper, thereby obtaining a 0.75 mm thick sheet with piles. of flakes.

About the obtained sheet-like material with piles, it dyed with a black dye under the temperature condition of 120 degreeC using a liquid flow dyeing machine. Next, it dried using a dryer to obtain a sheet having an average single fiber diameter of ultrafine fibers of 4.4 μm. The obtained sheet had a stiffness of 80 mm, a wear loss before the light resistance test of 7 mg, and a wear loss after the light resistance test of 9 mg, and had a soft feel and excellent light resistance and wear resistance. In addition, an N-acylurea bond and an isourea bond exist in the polymer elastomer. In addition, the L value retention rate was 93%, the heat resistance was excellent, and the amount of the inorganic salt containing monovalent cations in the polymer elastomer was lower than the detection lower limit.

[Example 2]

(non-woven fabric)

As in Example 1, the nonwoven fabric A for fibrous substrates was used as the nonwoven fabric.

(Addition of high molecular elastomer)

The heat-sensitive coagulant was changed to sodium chloride (represented as "NaCl" in Table 1). In addition, it carried out similarly to Example 1 except having changed the addition amount of the heat-sensitive coagulant, the heating temperature by hot air, and the application amount of the polymer elastomer, thereby obtaining a polymer elastomer-imparted nonwoven fabric.

(Extra-fine fiber display processing)

Except having changed the drying temperature, it carried out similarly to Example 1.

(Dyeing・Finishing)

It carried out similarly to Example 1. The obtained sheet had a stiffness of 90 mm, a wear loss before the light resistance test of 6 mg, and a wear loss after the light resistance test of 8 mg, and had a soft feel and excellent light resistance and wear resistance. In addition, an N-acylurea bond and an isourea bond exist in the polymer elastomer. In addition, the L value retention rate was 91%, the heat resistance was excellent, and the amount of the inorganic salt containing a monovalent cation in the polymer elastomer was lower than the detection lower limit.

[Example 3]

(non-woven fabric)

As in Example 1, the nonwoven fabric A for fibrous substrates was used as the nonwoven fabric.

(Addition of high molecular elastomer)

Except having changed the addition amount of a heat-sensitive coagulant, the heating temperature by hot air, and the application amount of a polymer elastomer, it carried out similarly to Example 1, and obtained the polymer elastomer application nonwoven fabric.

(Extra-fine fiber display processing)

Except having changed the drying temperature, it carried out similarly to Example 1.

(Dyeing・Finishing)

It carried out similarly to Example 1. The obtained sheet had a stiffness of 55 mm, a wear loss before the light resistance test of 12 mg, and a wear loss after the light resistance test of 18 mg, and had a soft hand and excellent light resistance and wear resistance. In addition, an N-acylurea bond and an isourea bond exist in the polymer elastomer. In addition, the retention rate of the L value was 97%, and it had excellent heat resistance, and the amount of the inorganic salt containing a monovalent cation in the polymer elastomer was lower than the detection lower limit.

[Example 4]

(non-woven fabric)

The nonwoven fabric B for fibrous substrates was used as the nonwoven fabric.

(Addition of high molecular elastomer)

Except having changed the heating temperature by hot air and the application amount of the polymeric elastomer, it carried out similarly to Example 2, and obtained the polymeric elastomer application nonwoven fabric with a thickness of 2.05mm.

(Extra-fine fiber display processing)

The obtained polymer elastomer-provided nonwoven fabric was immersed in a sodium hydroxide aqueous solution having a concentration of 8 g/L heated to a temperature of 95° C. for 10 minutes to remove the sea component of the sea-island type composite fiber. Then, the sodium hydroxide aqueous solution adhering to the nonwoven fabric was immersed in water, washed for 30 minutes, and dried with a dryer at 170° C. for 30 minutes to obtain a sheet (polymer elastic body-imparting sheet) containing ultrafine fibers.

(Dyeing・Finishing)

The obtained deseamed high-molecular elastomer-imparting sheet was half-cut in a direction perpendicular to the thickness direction, and the opposite side of the half-cut surface was ground with a circular sandpaper of No. 120 sandpaper, thereby obtaining a 0.75 mm thick sheet with piles. of flakes.

About the obtained sheet-like material with piles, it dyed with a black dye under the temperature condition of 120 degreeC using a liquid flow dyeing machine. Next, it dried using a dryer to obtain a sheet-like product having an average single fiber diameter of ultrafine fibers of 3.0 μm. The obtained sheet had a stiffness of 75 mm, a wear loss before the light resistance test of 7 mg, and a wear loss after the light resistance test of 10 mg, and had a soft hand and excellent light resistance and wear resistance. In addition, an N-acylurea bond and an isourea bond exist in the polymer elastomer. In addition, the retention rate of the L value was 96%, the heat resistance was excellent, and the amount of the inorganic salt containing monovalent cations in the polymer elastomer was lower than the detection lower limit.

[Example 5]

(non-woven fabric)

As in Example 1, the nonwoven fabric A for fibrous substrates was used as the nonwoven fabric.

(Addition of high molecular elastomer)

Except having changed the addition amount of a thermosensitive coagulant and thermosensitive coagulant, and the provision amount of a polymer elastomer, it carried out similarly to Example 1, and obtained the nonwoven fabric provided with a polymer elastomer.

(Extra-fine fiber display processing)

It carried out similarly to Example 1.

(Dyeing・Finishing)

It carried out similarly to Example 1. The obtained sheet had a stiffness of 100 mm, a wear loss before the light resistance test of 6 mg, and a wear loss after the light resistance test of 8 mg, and had a soft hand and excellent light resistance and wear resistance. In addition, an N-acylurea bond and an isourea bond exist in the polymer elastomer. In addition, the retention rate of the L value was 94%, and it had excellent heat resistance, and the amount of the inorganic salt containing monovalent cation in the polymer elastomer was lower than the detection lower limit.

[Example 6]

(non-woven fabric)

As in Example 4, the nonwoven fabric B for fibrous substrates was used as the nonwoven fabric.

(Addition of high molecular elastomer)

In the same manner as in Example 4, a polymer elastomer-imparted nonwoven fabric was obtained.

(Extra-fine fiber display processing)

It carried out similarly to Example 4.

(Dyeing・Finishing)

Both surfaces of the obtained high-molecular elastic body-imparting sheet after desealing were ground with a ring sandpaper of No. 180 sandpaper, thereby obtaining a 1.50 mm-thick sheet-like article with piles.

About the obtained sheet-like material with piles, it dyed with a black dye under the temperature condition of 120 degreeC using a liquid flow dyeing machine. Next, after drying with a dryer, half-cutting was performed in the direction perpendicular to the thickness direction to obtain a sheet having an average single fiber diameter of ultrafine fibers of 3.0 μm.

The obtained sheet had a stiffness of 80 mm, a wear loss before the light resistance test of 6 mg, and a wear loss after the light resistance test of 9 mg, and had a soft hand and excellent light resistance and wear resistance. In addition, an N-acylurea bond and an isourea bond exist in the polymer elastomer. In addition, the retention rate of the L value was 96%, the heat resistance was excellent, and the amount of the inorganic salt containing monovalent cations in the polymer elastomer was lower than the detection lower limit.

[Comparative Example 1]

(non-woven fabric)

As in Example 1, the nonwoven fabric A for fibrous substrates was used as the nonwoven fabric.

(Addition of high molecular elastomer)

With respect to 100 parts by mass of the polymer elastomer, 10 parts by mass of magnesium sulfate (referred to as "MgSO ₄ " in Table 1) as a heat-sensitive coagulant was added, 3 parts by mass of a carbodiimide-based crosslinking agent was added, and water The whole was prepared to have a solid content of 12% by mass, and an aqueous dispersion containing a polymer elastomer was obtained. However, during processing, gelation occurred on the surface of the nonwoven fabric, and the polymer elastomer could not be imparted to the nonwoven fabric.

[Comparative Example 2]

(non-woven fabric)

As in Example 1, the nonwoven fabric A for fibrous substrates was used as the nonwoven fabric.

(Addition of high molecular elastomer)

Except having changed the addition amount of the heat-sensitive coagulant, it carried out similarly to Example 1, and obtained the nonwoven fabric provided with a high molecular elastic body.

(Extra-fine fiber display processing)

It carried out similarly to Example 1.

(Dyeing・Finishing)

It carried out similarly to Example 1. Since the stiffness of the obtained sheet-like product was more than 150 mm, it could not be measured, and it had a hard feel. The wear loss before the light resistance test was 15 mg, and the wear loss after the light resistance test was 25 mg. In addition, an N-acylurea bond and an isourea bond exist in the polymer elastomer. In addition, the L value retention rate was 87%, the heat resistance was insufficient, and the amount of the monovalent cation-containing inorganic salt in the polymer elastomer was lower than the detection lower limit.

[Comparative Example 3]

(non-woven fabric)

As in Example 1, the nonwoven fabric A for fibrous substrates was used as the nonwoven fabric.

(Addition of high molecular elastomer)

Except having changed the addition amount of the heat-sensitive coagulant, it carried out similarly to Example 1, and obtained the nonwoven fabric provided with a high molecular elastic body.

(Extra-fine fiber display processing)

It carried out similarly to Example 1.

(Dyeing・Finishing)

It carried out similarly to Example 1. Since the stiffness of the obtained sheet-like product was more than 150 mm, it could not be measured, and it had a hard feel. The abrasion loss before the light resistance test was 16 mg, and the abrasion loss after the light resistance test was 28 mg, and the light resistance was a poor level. In addition, an N-acylurea bond and an isourea bond exist in the polymer elastomer. In addition, the L value retention rate was 89%, the heat resistance was insufficient, and the amount of the monovalent cation-containing inorganic salt in the polymer elastomer was below the detection lower limit.

[Comparative Example 4]

(non-woven fabric)

As in Example 1, the nonwoven fabric A for fibrous substrates was used as the nonwoven fabric.

(Addition of high molecular elastomer)

Except not providing a crosslinking agent, it carried out similarly to Example 2, and obtained the nonwoven fabric provided with a polymer elastomer.

(Extra-fine fiber display processing)

It carried out similarly to Example 2.

(Dyeing・Finishing)

It carried out similarly to Example 1. Since the stiffness of the obtained sheet-like product was more than 150 mm, it could not be measured, and it had a hard feel. The abrasion loss before the light resistance test was 21 mg, and the abrasion loss after the light resistance test was 32 mg, and the light resistance and abrasion resistance were poor. In addition, N-acylurea bond and isourea bond do not exist in the polymer elastomer. In addition, the L value retention rate was 88%, the heat resistance was insufficient, and the amount of the monovalent cation-containing inorganic salt in the polymer elastomer was lower than the detection lower limit.

[Comparative Example 5]

(non-woven fabric)

As in Example 1, the nonwoven fabric A for fibrous substrates was used as the nonwoven fabric.

(Addition of high molecular elastomer)

Except having changed the heating temperature, it carried out similarly to Example 1, and obtained the nonwoven fabric provided with a polymer elastic body.

(Extra-fine fiber display processing)

It carried out similarly to Example 1.

(Dyeing・Finishing)

It carried out similarly to Example 1. The stiffness of the obtained sheet was 120 mm, the abrasion loss before the light resistance test was 13 mg, and the abrasion loss after the light resistance test was 29 mg, and the light resistance was a poor level. In addition, an N-acylurea bond and an isourea bond exist in the polymer elastomer. In addition, the L value retention rate was 88%, the heat resistance was insufficient, and the amount of the monovalent cation-containing inorganic salt in the polymer elastomer was lower than the detection lower limit.

[Comparative Example 6]

(non-woven fabric)

As in Example 1, the nonwoven fabric A for fibrous substrates was used as the nonwoven fabric.

(Addition of high molecular elastomer)

In the same manner as in Example 1, a polymer elastomer-imparted nonwoven fabric was obtained.

(Extra-fine fiber display processing)

Except having changed the drying temperature, it carried out similarly to Example 1.

(Dyeing・Finishing)

It carried out similarly to Example 1. The stiffness of the obtained sheet was 130 mm, the abrasion loss before the light resistance test was 16 mg, and the abrasion loss after the light resistance test was 30 mg, and the light resistance was a poor level. In addition, an N-acylurea bond and an isourea bond exist in the polymer elastomer. In addition, the L value retention rate was 88%, the heat resistance was insufficient, and the amount of the monovalent cation-containing inorganic salt in the polymer elastomer was lower than the detection lower limit.

[Comparative Example 7]

(non-woven fabric)

As in Example 1, the nonwoven fabric A for fibrous substrates was used as the nonwoven fabric.

(Addition of high molecular elastomer)

With respect to 100 parts by mass of the polymer elastomer, 3 parts by mass of a carbodiimide-based crosslinking agent was added, and a nonionic thickening agent was added so that the active ingredient was 1 part by mass with respect to 100 parts by mass of the polymer elastomer agent (guar gum) [Taiyo Chemical Co., Ltd. "Neosoft G"], and the whole was prepared with water to give a solid content of 13% by mass, thereby obtaining an aqueous dispersion containing a polymer elastomer. The obtained nonwoven fabric was immersed in the aforementioned aqueous dispersion, and then treated in hot water at a temperature of 90° C. for 3 minutes, followed by hot-air drying at a drying temperature of 160° C. for 30 minutes to obtain a sheet-like product so as to be formed into a sheet-like product. The polymer elastomer provided nonwoven fabric with a thickness of 2.10 mm in which the polymer elastic body was provided so that the polymer elastic body in 100 mass % was 20 mass %.

(Extra-fine fiber display processing)

It carried out similarly to Example 1.

(Dyeing・Finishing)

It carried out similarly to Example 1. The stiffness of the obtained sheet was 90 mm, the abrasion loss before the light resistance test was 20 mg, and the abrasion loss after the light resistance test was 33 mg, and the light resistance and abrasion resistance were poor. In addition, an N-acylurea bond and an isourea bond exist in the polymer elastomer. In addition, the L value retention rate was 87%, the heat resistance was insufficient, and the amount of the monovalent cation-containing inorganic salt in the polymer elastomer was lower than the detection lower limit.

[Comparative Example 8]

(non-woven fabric)

As in Example 1, the nonwoven fabric A for fibrous substrates was used as the nonwoven fabric.

(Addition of high molecular elastomer)

Except not providing a crosslinking agent, it carried out similarly to Example 2, and obtained the nonwoven fabric provided with a polymer elastomer.

(Extra-fine fiber display processing)

The obtained polymer elastomer-provided nonwoven fabric was immersed in a sodium hydroxide aqueous solution having a concentration of 8 g/L heated to a temperature of 95° C. and treated for 5 minutes, thereby removing the sea component of the sea-island type composite fiber. Next, the sodium hydroxide aqueous solution adhering to the nonwoven fabric was immersed in water, washed for 30 minutes, and dried with a dryer at 120° C. for 30 minutes. Then, a carbodiimide-based crosslinking agent was added to water, the entire crosslinking agent adjusted to a solid content of 2% by mass was impregnated and applied to the sheet, and dried with a dryer at 160° C. for 30 minutes, thereby obtaining an ultrafine Fiber sheet (polymer elastomer-imparting sheet).

(Dyeing・Finishing)

It carried out similarly to Example 1. Since the stiffness of the obtained sheet-like product was more than 150 mm, it could not be measured, and it had a hard feel. The abrasion loss before the light resistance test was 20 mg, and the abrasion loss after the light resistance test was 30 mg, and the light resistance and abrasion resistance were poor. In addition, an N-acylurea bond and an isourea bond exist in the polymer elastomer. In addition, the L value retention rate was 86%, the heat resistance was insufficient, and the amount of the monovalent cation-containing inorganic salt in the polymer elastomer was lower than the detection lower limit.

[Comparative Example 9]

(non-woven fabric)

As in Example 4, the nonwoven fabric B for fibrous substrates was used as the nonwoven fabric.

(Addition of high molecular elastomer)

The nonwoven fabric was impregnated with a 10% by mass aqueous solution of PVA (NM-14, manufactured by Nippon Synthetic Chemical Co., Ltd.) having a degree of saponification of 99% and a degree of polymerization of 1400, followed by heating and drying at a temperature of 140° C. for 10 minutes to obtain a solution of The nonwoven fabric for fibrous substrates is a PVA-imparting sheet with an adhesion amount of PVA of 30 parts by mass relative to 100 parts by mass of fibers.

The obtained PVA-imparting sheet was immersed in a sodium hydroxide aqueous solution having a concentration of 8 g/L heated to a temperature of 95° C. and treated for 30 minutes, thereby obtaining a sheet (PVA) containing sea-based ultrafine fibers from which the sea-island composite fibers were removed. Endowed with ultrafine fiber non-woven).

With respect to 100 parts by mass of the macromolecular elastomer, 15 parts by mass of sodium chloride (referred to as "NaCl" in Table 1) was added as a heat-sensitive coagulant, 3 parts by mass of a carbodiimide-based crosslinking agent was added, and the mixture was mixed with water. The whole was prepared to have a solid content of 12% by mass, thereby obtaining an aqueous dispersion liquid containing a high molecular elastomer. The thermal coagulation temperature is 68°C. The obtained nonwoven fabric A for a fibrous base material was immersed in the aforementioned aqueous dispersion, and then dried with hot air at a temperature of 160° C. for 20 minutes to obtain a sheet-like product with a high percentage of 100% by mass in the sheet-like product. A 2.05-mm-thick polymer-elastomer-providing sheet in which a polymer elastomer was provided so that the molecular elastomer was 38% by mass.

The obtained polymer elastomer-imparting sheet was immersed in water heated to 95° C., treated for 10 minutes, and dried with a dryer at 120° C. for 30 minutes to obtain a sheet from which the applied PVA was removed.

(Dyeing・Finishing)

It carried out similarly to Example 1. The stiffness of the obtained sheet was 90 mm, the abrasion loss before the light resistance test was 11 mg, and the abrasion loss after the light resistance test was 26 mg, and the light resistance was a poor level. In addition, an N-acylurea bond and an isourea bond exist in the polymer elastomer. In addition, the L value retention rate was 91%, and it had excellent heat resistance, and the amount of the monovalent cation-containing inorganic salt in the polymer elastomer was 1.2% by mass.

[Comparative Example 10]

(non-woven fabric)

As in Example 6, the nonwoven fabric B for fibrous substrates was used as the nonwoven fabric.

(Addition of high molecular elastomer)

Except having changed the heating temperature, it carried out similarly to Example 6, and obtained the polymeric elastomer provision nonwoven fabric.

(Extra-fine fiber display processing)

Except having changed the drying temperature, it carried out similarly to Example 6.

(Dyeing・Finishing)

It carried out similarly to Example 6. The stiffness of the obtained sheet was 85 mm, the abrasion loss before the light resistance test was 21 mg, and the abrasion loss after the light resistance test was 31 mg, and the light resistance and abrasion resistance were poor. In addition, an N-acylurea bond and an isourea bond exist in the polymer elastomer. In addition, the L value retention rate was 85%, the heat resistance was insufficient, and the amount of the monovalent cation-containing inorganic salt in the polymer elastomer was below the detection lower limit.

[Table 1]

[Table 2]

In addition, "PU" in Table 2 represents polyurethane.

Industrial Availability

The sheet-like product obtained by the present invention can be suitably used for furniture, chairs and wall materials, seats in vehicle interiors such as automobiles, trains, and aircrafts, ceilings, and interior decorations having a very elegant appearance as skin materials for interior decorations and the like materials; uppers, trims, etc. of shoes such as shirts, jackets, casual shoes, sports shoes, men's and women's shoes, etc.; bags, belts, wallets, etc.; Abrasive cloth and CD curtain and other industrial materials.

Claims (8)

1. A sheet, which is a sheet containing a polymer elastomer in a fibrous base material, the fibrous base material contains ultrafine fibers with an average single fiber diameter of 0.1 μm or more and 10 μm or less, and the polymer elastomer has hydrophilic properties; The polymer elastomer has an N-acylurea bond and/or an isourea bond inside, and the sheet-like product satisfies the following conditions 1 and 2, Condition 1: The stiffness in the longitudinal direction specified in the A method (45° cantilever method) described in JIS L 1096:2010 "Woven and Knitted Fabrics" is 40 mm or more and 140 mm or less, Condition 2: The Martindale abrasion test specified in JIS L 1096: 2005 after the light resistance test measured under the condition that the xenon arc amount of JIS L 0843: 2006 color fastness measurement method is 110 MJ/m ² is 20,000 times The wear loss at this time is 25 mg or less. 2 . The sheet-like article according to claim 1 , wherein the sheet-like article before the light resistance test has an abrasion loss of 20 mg or less when the Martindale abrasion test specified in JIS L 1096:2010 is 20,000 times. 3 . 3. The sheet-like product according to claim 1 or 2, comprising 10% by mass or more of the polymer elastomer. 4. The sheet-like article according to any one of claims 1 to 3, wherein the sheet-like article further satisfies the following condition 3, Condition 3: The raised surface of the sheet was placed on a hot plate heated to 150° C., and the retention rate of the L value when pressed with a pressing load of 2.5 kPa for 10 seconds was 90% or more and 100% or less. 5. A method for producing a sheet, comprising the following steps (1) to (4) in this order, (1) A polymer elastomer impregnation step in which a fibrous base material containing ultrafine fiber-developing fibers is impregnated with an aqueous dispersion, followed by heat treatment at a temperature of 120° C. or higher and 180° C. or lower, and the aqueous dispersion liquid is Contains a polymer elastomer, a monovalent cation-containing inorganic salt, and a cross-linking agent, wherein the polymer elastomer has a hydrophilic group and contains a polyether diol as a constituent, relative to the polymer elastomer 100 parts by mass, the content of the monovalent cation-containing inorganic salt in the aqueous dispersion is more than 10 parts by mass and less than 50 parts by mass; (2) an ultrafine fiber development step, wherein the ultrafine fiber development type fibers are subjected to alkali treatment to develop the ultrafine fibers; (3) a drying step, wherein heat treatment is performed at a temperature of 120°C or higher and 180°C or lower; (4) Raising process in which at least one surface of the non-raised sheet-like object is subjected to a raising treatment to form piles on the surface. 6 . The method for producing a sheet according to claim 5 , further comprising a dyeing step of dyeing a non-fluffed sheet or a sheet after the drying step. 7 . 7 . The method for producing a sheet-like product according to claim 5 , wherein the monovalent cation-containing inorganic salt is sodium chloride and/or sodium sulfate. 8 . The manufacturing method of the sheet-like object in any one of Claims 5-7 whose said crosslinking agent is a carbodiimide type crosslinking agent.